Wetting agents for aqueous alkalizing liquids



WETIING AGENTS FOR AQUEOUS ALKALIZING LIQUIDS Kurt Hofer, Neue Welt, Muncheu'stein, Switzerland, as-' signor, by mesne assignments, toSaul & Co., Newark, NJ., as nominee of Fidelity Union Trust Company executive trustee under Sandoz Trust I No Drawing. Application February 24, 1954 Serial No. 412,387

Claims priority, application Switzerland March 6, 1953 The present invention relatesto aqueous alkalizing liquids. a

These wetting agents are prepared, according to the invention, by the action of alkali metal'sulfite on halogen hydrins'of-monoalkyl ethers of glycerol, the alkyl group containing 5 to 7 carbon atoms, or on the correspond-j ing epoxides, and if desired admixing the reaction mixture or the obtained reaction products with ether alcohols. The halogen hydrins are advantageously prepared from the corresponding alcohols containing 5 to 7 carbon atoms. in the molecule, such for example as isoamyl alcohol, 2-

amyl alcohol, n-hexyl alcohol, 'Z-ethylbutyl alcohol, -.n1ethyl-amyl alcohol, .3-heptyl alcohol, etc., aswell as mixtures of these alcohols, and epichlorhydrin, and the wetting agents .for a.

ethers, such as are obtained by the addition of two and more mols of epichlor hydrin onto one vmol of b'utyl alco:

liol', amyl alcohol or hexyl alcohol and subsequentiboilingl with diluteaqueous caustic alkali. i Depending upon the particular use in view for the,

aforesaid ether-sulfonic acid salts and the mixtures thereof with ether alcohols, suitable further auxiliary agents may be" added Ithereto, such for exampleas phenols or naphthe'nic acids which enhance the wettingfactiomor' aliphatic or cycloaliphatic hydrocarbons,"such astho'se with boiling points in the range of'1 5(l250 C., or aim,

hols such for example as those containing'5 to 12 car-f bon atoms in the moleculejwhich enhancethe Wetting action and also suppress undesired foaming action;

Phosphoric aciddria'lkyl esters and organic silicon corn:

pounds are also suitable to suppress foaming action.

The wetting agents. of the. present invention are particularly suitable for use in alkaline textile treating baths,

such as are employed in the'mercerization and alkaliza; tion of cellulose and regenerated cellulose, i.e. in aqueous caustic alkali solutions of 20 to 40- B. aswell a sQinf weaker lyes, which solutions .mayalso contain common salt (sodium chloride) or soda (sodium carbonate);

The following examples set forth presently-preferred illustrative embodiments of the invention. In these e'xamples, the parts and "percentages,-unless otherwise indiepoxides are prepared fromthe thus-obtained chlorhy- -drinsiby the splitting ofi-of hydrochloric acid, known a y The reawtion with the alkali metal sulfite-advantageously takes place in known manner in aqueous s'olution or'suspension at ordinary orelevatedpressure andlateleva'ted 5] temperature'l Neutral sulfitesareipfferzibly;employed when starting: with halogen hydrin's; fFor reactionwith the "epoxides, the acid sulfites, suchas 'sodiumirbi'sulfite or potassium bisulfite, are bettersuited. e 1 lnthereactioh with the alkalfmetal sulfites; thereare' formed alkalimetalsalts of the compound,

cated, are ,by weight; the -temperatures are .in degrees centigrade.

; zssipr'ts of epichlorhydrin are added 'sio 1y,1ah11e stirring, .to 22p parts of isoamyl alcohol and? 1 part byweight ofjboron fluoride etlle'rateg and theni stirringi s continued for several more hours at 85 when a test specimen of the reaction product-is distilled under i'eov duced pressure, it will be found that'all theepichlorhydr in has reacted and that only a very small quantity ofunor isomers thereof or condensation productslof these ether alcohols with ;the corresponding halogenhydrins orzepoxides. The formation of, such secondaryproducts is of particular advantage where the isulfonic acids or the salts thereof have a tendency toward crystallization; the -presence...of. such ether lalcohols acting to. fslow p or entirely to prevent the crystallization. In addition,

the wetting action is enhanced by such etheralcohols' In faj: t,' in some cases itlis advantageous to addito, the

reaction products ether alcohols, such for? example as I sulfite is present. ,The solution' containsa and about 8% of ether-like condensation product of epij ring to6SQ -parts of an aqueous sodium;ibisnliite 1. of. 30% strength '221,853,,:andistirring isithenicontiriu for 6 hours at this temperature.- Aclea'r, yell'o changed isoamyl alcohol is still present. Thegcl'udfl chlorhydrin ether is'then treated for- 4 hours at 30-40 with 260 parts-of aqueous caustic soda solution of 50% sodium chloride, the crude epoxide'is easilyris'olatedgas a thinly fluid oil; In'addition to the. primary productjofi per cubic centimeter), there isals'o present primarily the compound of the formula I (CHt)2CH-OH1CHrf-0CH CH CH2CL i I W: i

' r ,CH'zI-CH .1-'CH| 1 1. Approximately 365 parts, of crudeL ePQ ideQare'ob The crude epoxide is then added slowlyai'id ish solution results. Titration with tenth-no maliodln solution indicates that .lessi'than 0.5%"of the sodium salt f i m l x' 'pr'v an w theformula Y (Carmen-on chlorhydrin with isoamyl alcohol (isoamyl ethers of glyceroll diglycerol), the remainder,oftl esolution'being water." a One-Percent by ol m shej a i qlit e ass a r-issue tarsus seat as. of 2a B. Raw thread fame" is vV't'td through and through" by the resultant barium salt of i's'oarnyloxypropanolsulfonic acid is pre-v cipitated. One gram of this barium salt yields, on addition of sulfuric acid, 0.395 gram of BaSO (theory 20,396 ram ,7 The pure isoarriyloxyp'ropanolsulfonic acid sodium salt is also a good. wetting agent in aqueous caustic soda liquor of 2030 B6; in" liquors of 26v Be. and over, it a tendency to crystallize out.

Instead of epichlorhydr'in an equimolecula'r quantity of bromhydrin may be used.

EXAMPLE 2 The sodium salt of n-amyloxypropanolsulfonic acid is prepared as an" aqueous solution of about 45% strength froi'nn amyl alcohoLafter the manner described for the is oaniyl" derivative inExample 1. One per cent by volume of the thus obtained solution is added to a mercerizing liquor of 28? B., whereby a good wetting capacity is imparted to the latter.

EXAMPLE 3 Z-p'entyIOXYchIorOprOpanol is obtained from pentanol- 2 by reaction with epichlorhydrin, after the manner described in Example 1 fof the reaction between epichlorhydrin ,and isoamyl alcohol. 7 other (550' parts). is then stirred for 12 hours at 90 With-1000 parts of an aqueous sodium sulfite solution of 25% a strength. A clear; slightly yellowish solution, which contains about 40% of the sodium salt of Z-pentyloxypropanol sulfonicacid oni 'onl on,

oH-ooHEo'HoH-omsoom CH: obtained; An addition of 1- to 1 .5% by volume of this solution to" an aqueous caustic soda or caustic potash solution of 20=-30 B. very greatly increases the wetting capacity thereof.

The reaction with the sodium sulfite proceeds more rapidly, and a product with even higher wetting capacity is obtained, if it is carried out in the presence of 100 of diethylene glycol-mono-n-butyl ether.

EXAMPLE 4 1 mol of a" technical amyl alcohol mixture is reacted in the: presence of a small quantity of boron fluoride at 80 with 1.4 mols of epichlorhydrin. The resultant crude chlorhydrin ether is then stirred with two mols of sodium hydroxide (in the form of aqueous caustic soda solution of 38% strength) for 5 hours at 30-40. A chlorinecontaining epoxidemixture is obtained, which is reacted fiis'jt with 0.8 mol of sodium bisulfite (in the form of an aqueous solution of 30% strength) for'4 hours at 85, after which an additional 0.5 mol of NaOH (aqueous solution of 30% strength) is added to the clear solution which is'th'ri boiled for '2 hours under reflux. In this wa the epoxide' rings are first split open with addition of NaHSO and then the chlorine atoms still present are replaced by OH-groups. A very active wetting agent which is readily soluble in caustic liquors of -32" B6. is thusv obtained.

7 EXAMPLE 5 one mol of epichlorhydriri is reacted with 3 m lser methr amy ...alq hql i eth l sqbutyl b al) 5 in the presence of a small quantity of boron fluoride.

the crude sodium salt of The crude chlorhydrin Shrinkage after:

. tends to crystallize out.

The excess of methylamyl alcohol is, distilled off under redueempressn're; Bind. practically" pure" arethylamylzrxy chloropropanol is obtained. This is stirred for- 6 hours at 30-35 with 1.8 mols of sodium hydroxide (aqueous caustic sodasolution of- 50% strength), and the methylainyldxypropoxide CH3 CH3 7 r CH-CHI GH I CH3 OCHzCH--CH:

(which boils at 89-91 under a'p'ressur'e'ofi 15mm. Hg) is obtained. The latter is reacted for 5 hours at 90 with one mol of sodium bisulfi'te (as an aqueous solution of 30% strength), while stirring. A clear solution of the sodium salt of methylarnyloxypropanolsulfonic acid on. CH3

/CH:CHa-OH CH3 OCHn-*'C-HOH-CH2SO:N8 is obtained. By evaporation, the salt is obtained in the form of white crystals.

To a solution of 27 grams ofthe said salt in cc. of water, there are added 250 grams of an aqueoussolution of BaClg-ZHgO of 10% strength. The white barium salt of the sulfonic acid is forthwith precipitated. After filteringoff the precipitate with suction and after'drying,

about 30 grams oi the barium salt of methylamyloxy a the extent of about,1%,- and can be recrystallized from hot water. 'One gram of the recrystallized and dried barium' salt is" dissolved in 100 cc. of boiling water; and

thenlO cc. of sulfuric acid (10% strength) are addedi Ba'SO precipitates which, after filtering ofiiand drying, isweighed; it amounts to 0.375 .gram (calculated: 0.378

The sodiurr'i salt issoluble in caustic liquors of 20- 32 Be. and, even when addedin small quantities- (2 to 4 grams per liter), imparts "very good wetting action thereto. In liquors of 26 B.- and over, the sodium salt By the addition of for example 5 to 20% of an ether alcohol,- such as dimethylene'gl'ycolmono-n-butyl ether or glycerol-mono-isoamyl ether, the

5 can 10 sen 15 son V 30 45 sec 60 sec.

g clear. I after 21 hrs"... crystallized V out.

EXAMPLE 6 1 a151 of inethylalilyl alcohol is reacted with 1.; man of pichlorhydr'in at 80 inthe resence ofboron fluoride serene, and men names was 2 111018 of a ueous sbdium" obtained, as in Example 1,, a mixture of methylamylpropenoxide with chlorine-containingcondensation products. This mixture is" reacted at 85-95flwith ;8 molof aqueous sodium bisulfite "solution (30%, strength) for 6 hours, with the addition of 0.2 molofsodium carbonate. A product is thus obtained'which is readily soluble I hydroxide solutionof 30% strength at. 30. There is 2. An alkaline solution for treating textile fibers consisting essentially of an aqueouscaustic alkalisolution in caustic liquors and which contains about 10% of methylamyl ethers of glycerol, diglycerol andhigher con-j densation products, in addition to about 45% ,offfthe sodium salt of methylamyloxypropanolsulfonic' acid.

Added to caustic liquors, of 20-32" B. in amounts of 0.4 to 0.8 percent by volume, the product imparts very goodwetting actiontthe'reto. 'Theresultantcaustic solutions are stable and show no tendency toward crystallization.

';A mixture of the obtained solution with f (by weight) of hexyleneglycol and 5% (by weight) of diisohutyl'carbinol produces a still more enhanced wetting action, and liquors prepared therewith practically do not EXAMPLE .7, l The procedure according toExample 6 is repeated except that the methylamyl alcohol is replaced by 2-ethylin addition to the corresponding glycerol ethers, 1% by a volume of the obtained solutionis'added to' a mercerilzing Q. i liquor of 28 B. "(Raw undes ized'thread fabric L is fwe'tted;

' through inabout '5' seconds byithe thus-amplifiedliquo' EXAMPLE 8 Heptanol- 3 is reactedfafteri the jmannerfldescribedlin d Example 6,-with epichlorhydrinfand caustic soda to-prowherein M stands for analkalimetal.

duce fi-heptyloxypropenoxide l anti n stands for an alkali unde sized cotton is greatly encncmcm-owmcnd" wa on f:

of -20 to 40 B containing dissolved therein less than 2% by volume of a compound of the formula CHr-CHFCH:

CHOCHIGHOHCHPSmM wherein M stands for an alltali metals 3. An alkaline solution for treating textile fibers con-.

sisting, essentially of an aqueous caustic alkali solution of 20to 40 B. containing dissolved therein less than 2% by volume of a compound of the formula wherein M stands for an alkali metal. 7

4. An alkaline solution for treating textile fibers consisting essentially of an aqueous caustic, alkali solution of '20 to 40 B containing dissolved therein less than 2% by volume ofa compound of the formula ROCH C HOHCHQSO M wherein R is a member selected from the group consisting of n-amyl, iso-amyl and secondary amyl groups, and M stands for an alkali metal.

5. A compound of the formula R Q- CH CHOHCH SO M wherein'R is a member selected fromthe group consisting 7 1d of n-amyl, iso-amyl and secondary amyl groups, and M i standsfor an alkalimetal. j

6. compound 'of the formula p cnaecm -cmcnpcnko cmcnoncn soam wherein M -stands forjan alkali metal. 1 f ff. j 7. ':A Compound of 'the formula i t r cncmcH,o cHlcHoHcHr-sonvr 8. A compound-of the formula cHr-cHr-cn, cnocnicnonom-soaM CH: I

wherein M stands for an alkali metal.

7 LA, mixture of pafts of. the obtained solution with j 5 a parts of hexaethylene 7 glycol-monododecyl ether is- I also a suitable.wettingagent'forian aqueous caustic 'soda, solution of 5 f B., such as-is used;in the manufacturei '1. An alkaline solution" forgtreating'Ltegttilefibers'con l sisting' essentiallyof' an aqueouscaustic alkali solutioni, of 20' to 40,B. containingdissolyed thereinless" 2% byivolume of a compound'ofthe foirnula i that v References Citedin'the file of this patent V UNITED STATES PATENTS 1,897,741 Ulrich-et'al. Feb. 14, 1933 1,985,747 Steindrof et al. Dec.-25, 1934 2,010,176 v 'Brodersen Aug. 6, 1935 2,033,125 Downing et al. Mar. 10, 1936 2,094,489 Hueter et al Sept. 28,1937

,, Smith Sept. 16, 1947 

4. AN ALKALINE SOLUTION FOR TREATING TEXTILE FIBERS CONSISTING ESSENTIALLY OF AN AQUEOUS CAUSTIC ALKALI SOLUTION OF 20 TO 40* BE CONTAINING DISSOLVED THEREIN LESS THAN 2% BY VOLUME OF A COMPOUND OF THE FORMULA 